Polymorphism in an unexpected caesium complex of 5-hydroxy­hydurilic acid

Nichol, G.S.; Clegg, W.

doi:10.1107/S0108270105029318

metal-organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 61| Part 10| October 2005| Pages m459-m462

doi:10.1107/S0108270105029318

Polymorphism in an unexpected caesium complex of 5-hydroxyhydurilic acid

Gary S. Nichol ^a and William Clegg ^a ^*

^aSchool of Natural Sciences (Chemistry), Bedson Building, University of Newcastle, Newcastle upon Tyne NE1 7RU, England
^*Correspondence e-mail: w.clegg@ncl.ac.uk

(Received 14 September 2005; accepted 15 September 2005; online 30 September 2005)

Vigorous reaction of barbituric acid with caesium hydroxide in water resulted in an unexpected coupling product, 5-hydroxyhydurilic acid, complexed to caesium, giving poly[[caesium-μ₅-5-hydroxyhydurilato] hemihydrate], {[Cs(C₈H₅N₄O₇)]·0.5H₂O}_n. This was obtained in two different polymorphic forms, depending on the method of crystal growth. Slow solvent evaporation yielded an orthorhombic polymorph, (I), which crystallized in the space group Pnab (non-standard setting of Pbcn), with the uncoordinated water molecule lying on a crystallographic twofold axis. The water molecule is sandwiched into cavities within the structure and is securely held in place by N—H⋯O and O—H⋯O hydrogen bonding. Polymorph (II) is monoclinic, although the unit-cell parameters are similar to those of polymorph (I), and it crystallizes in the space group C2/c, with the uncoordinated water molecule again lying on the twofold axis and secured by hydrogen bonding. The differences between the two polymorphs, both of which have nine-coordinate caesium and a similar first-shell environment of all structural components, are in the overall arrangement of the cations, anions and water molecules, and in the shape of the cavities, revealed by inspecting and comparing crystal-packing diagrams.

Comment

Barbituric acid is a simple molecule which has been much studied in recent times due to its propensity to form polymorphs and, as a result, it has been used as a model compound for developing computational polymorph prediction techniques (Lewis et al., 2004 ). One of the major obstacles to the success of this research has been the partial flexibility of the molecule, which makes successful polymorph modelling particularly tricky (Lewis et al., 2005 ). Recently, we demonstrated that this molecular flexibility allows the crystal structure of barbituric acid dihydrate to undergo a phase transition at low temperatures (Nichol & Clegg, 2005 ).

acid (5-hydroxy-5,5′-bibarbituric acid) (see scheme

), which coordinated in its anionic form to caesium. Repeating the reaction but with only brief heating of the reaction solution gave a normal barbiturate complex, as for the other alkali metals. We have also observed this same coupling when 1,8-bis(dimethylamino)naphthalene (a proton sponge) was used as the base in a methanolic solution of barbituric acid, so the actual base and solvent used would not seem to be determining factors for the reaction. 5-Hydroxyhydurilic acid itself is rather unusual; it is not commercially available and the only reported synthesis to date is by electrochemical oxidation of hydurilic acid (and so not actually a barbiturate coupling reaction; Kato et al., 1975

Crystallization of the reaction product gave two polymorphic forms, (I) and (II). Crystallization by slow solvent evaporation gave polymorph (I) in the orthorhombic space group Pbcn (reported here in the alternative setting Pnab, so that the axes match those in the second polymorph); the space group determination was unambiguous from the systematic absences. The structural unit of polymorph (I) is presented in Fig. 1 and is twice the size of the asymmetric unit. It consists of two caesium–5-hydroxyhydurilate complexes related by a twofold rotation about a non-coordinated but hydrogen-bonded water molecule. The water molecule acts as a donor in two O—H⋯O interactions and as an acceptor in two N—H⋯O interactions (Table 2) and so is pseudo-tetrahedral. Additional intramolecular hydrogen bonding secures the location of the OH group into an S(6) ring (Bernstein et al., 1995 ). The Cs ion is nine-coordinate (not shown in full in Fig. 1) and the Cs—O bond lengths range from the relatively short 2.981 (2) Å to the rather long 3.531 (2) Å (Table 1). One of the rings of the 5-hydroxyhydurilate ligand is essentially planar (r.m.s. deviation from a mean plane fitted through the non-H atoms is 0.012 Å), as is usually observed in deprotonated barbituric acid, whilst the second ring contains an sp³-hybridized C atom, which is displaced slightly out of the ring of the remaining non-H atoms (r.m.s. deviation 0.078 Å); the angle between the two mean planes is 85.6 (2)°. The two new bonds formed in the coupling reaction are C4—C5 and C4—O7, which have lengths of 1.502 (4) and 1.439 (3) Å, respectively, indicating that both are single bonds. The hydroxy H atom was easily located in a difference electron-density map, confirming that the C4—O7 bond is single in character. In the planar ring, bonding is delocalized over the O4—C6—C5—C8—O6 segment, with each bond intermediate between single and double.

A monoclinic polymorph, (II), was obtained by storing the solution at approximately 278 K for several months. Although the unit-cell parameters of polymorph (II) are similar to those of polymorph (I), this is for a C-centred rather than a primitive unit cell. The structural unit of polymorph (II) is shown in Fig. 2. Like polymorph (I), polymorph (II) crystallizes with one non-coordinating water molecule on a twofold rotation axis, and so the asymmetric unit is one half of the structural unit. Also, as in polymorph (I), the water molecule is secured in place by four hydrogen bonds, as donor for two and as acceptor for the other two, with additional intramolecular hydrogen bonding securing the position of the hydroxy H atom (Table 4). The Cs ion is again nine-coordinate, but the range of bond lengths is much wider, from 2.983 (4) to 3.690 (4) Å (Table 3), which is distinctly long for a Cs—O bond, but not unknown. The two 5-hydroxyhydurilate rings are either essentially planar (r.m.s. deviation 0.007 Å for one) or slightly distorted (r.m.s. deviation 0.090 Å for the other), as is seen in polymorph (I), although in polymorph (II), the angle between their two mean planes is slightly smaller, at 78.3 (2)°. Also in common with polymorph (I), the C4—C5 and C4—O7 bond lengths are 1.531 (6) and 1.421 (6) Å, respectively, indicating single-bond character.

If the individual structural units of polymorphs (I) and (II) give little indication that these are two different polymorphic structures, then their respective packing diagrams are more revealing. Fig. 3 shows two b-axis projections of polymorphs (I) (top) and (II) (bottom). Setting polymorph (I) in space group Pnab allows a direct comparison to be made between the two, as the cell axes are now approximately equal. Both are three-dimensional structures featuring columns of quadruply bridged Cs centres. These columns are then linked together by further coordination from the second ring of the ligand across to a Cs centre of another column. This linkage creates what appear to be channels within the structure, sandwiched inside which are securely hydrogen-bonded pseudo-tetrahedral water molecules. Inspection of space-filling models, however, shows that the water molecules lie in individual cavities, between which there are only restricted openings. The differences between the two packing diagrams are in the overall arrangement of the cations, anions and water molecules, and in the shape of the cavities. These are most easily seen by concentrating on the water-filled cavities. In polymorph (I), these apparent channels are arranged such that the overall impression is one of `ripples' within the structure along the c axis. In polymorph (II), there is no such rippling and the apparent channels are stacked ladder-like in a regular rectangular grid.

Figure 1
The structural unit of polymorph (I)

, shown with 50% probability displacement ellipsoids. Dashed lines indicate selected hydrogen bonds.

Figure 2
The structural unit of polymorph (II)

, shown with 50% probability displacement ellipsoids. Dashed lines indicate selected hydrogen bonds.

Figure 3
Packing diagrams, projected along the b axes, for polymorphs (I)

(top) and (II)

(bottom).

Experimental

CsOH·H₂O (0.171 g, 1 mmol) and barbituric acid (0.132 g, 1 mmol) were dissolved in distilled water (approximately 30 ml), and the solution was boiled until approximately 10 ml remained. Slow evaporation of a small amount of solvent over a period of one week yielded some very small crystals of polymorph (I). Storage of the solution at approximately 278 K for around five months yielded small crystal clusters of polymorph (II).

Polymorph (I)

Crystal data

[Cs(C₈H₅N₄O₇)]·0.5H₂O
M_r = 411.08
Orthorhombic, P n a b
a = 13.6671 (8) Å
b = 7.0632 (4) Å
c = 23.5991 (17) Å
V = 2278.1 (2) Å³
Z = 8
D_x = 2.397 Mg m⁻³
Mo Kα radiation
Cell parameters from 19019 reflections
θ = 2.5–27.5°
μ = 3.30 mm⁻¹
T = 150 (2) K
Block, colourless
0.30 × 0.10 × 0.10 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.681, T_max = 0.723
49241 measured reflections
2592 independent reflections
2146 reflections with I > 2σ(I)
R_int = 0.065
θ_max = 27.5°
h = −17 → 17
k = −9 → 8
l = −30 → 30

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.047
S = 1.05
2592 reflections
204 parameters
Only H-atom coordinates refined
w = 1/[σ²(F_o²) + (0.0137P)² + 4.4877P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected geometric parameters (Å, °) for polymorph (I)

Cs—O1	3.352 (2)
Cs—O2ⁱ	3.2119 (19)
Cs—O3ⁱⁱ	3.1808 (19)
Cs—O4ⁱⁱⁱ	3.1361 (19)
Cs—O4ⁱⁱ	3.469 (2)
Cs—O5^iv	2.981 (2)
Cs—O5^v	3.320 (2)
Cs—O6	3.531 (2)
Cs—O7^vi	3.040 (2)
O4—C6	1.267 (3)
O6—C8	1.253 (3)
O7—C4	1.439 (3)
C1—C4	1.542 (4)
C3—C4	1.530 (4)
C4—C5	1.502 (4)
C5—C6	1.395 (4)
C5—C8	1.399 (4)

C1—C4—C3	113.3 (2)
C6—C5—C8	120.7 (2)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y, -z]$ ; (ii) $[x-{\script{1\over 2}}, -y+1, z]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) x, y-1, z; (vi) $[x-{\script{1\over 2}}, -y, z]$ .

Table 2
Hydrogen-bond geometry (Å, °) for polymorph (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7⋯O4	0.93 (3)	1.65 (3)	2.563 (3)	164 (3)
O8—H8⋯O6	0.72 (3)	2.08 (3)	2.780 (3)	163 (4)
N1—H1N⋯O8^v	0.74 (3)	2.16 (3)	2.865 (3)	161 (3)
N2—H2N⋯O3^vii	0.73 (3)	2.09 (3)	2.816 (3)	174 (3)
N3—H3N⋯O1^viii	0.75 (3)	2.57 (3)	3.151 (3)	136 (3)
N4—H4N⋯O7ⁱⁱ	0.82 (3)	2.29 (3)	3.005 (3)	147 (3)
Symmetry codes: (ii) $[x-{\script{1\over 2}}, -y+1, z]$ ; (v) x, y-1, z; (vii) -x+1, -y+1, -z; (viii) $[x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Polymorph (II)

Crystal data

[Cs(C₈H₅N₄O₇)]·0.5H₂O
M_r = 411.08
Monoclinic, C 2/c
a = 12.1244 (16) Å
b = 8.1353 (11) Å
c = 23.267 (3) Å
β = 91.654 (2)°
V = 2294.0 (5) Å³
Z = 8
D_x = 2.381 Mg m⁻³
Mo Kα radiation
Cell parameters from 7338 reflections
θ = 3.0–28.2°
μ = 3.28 mm⁻¹
T = 150 (2) K
Block, colourless
0.30 × 0.18 × 0.15 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Thin-slice ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003)T_min = 0.494, T_max = 0.612
10061 measured reflections
2765 independent reflections
2661 reflections with I > 2σ(I)
R_int = 0.031
θ_max = 28.2°
h = −16 → 15
k = −10 → 10
l = −30 → 30

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.082
S = 1.42
2765 reflections
204 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + 28.7093P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 1.49 e Å⁻³
Δρ_min = −2.50 e Å⁻³

Table 3
Selected geometric parameters (Å, °) for polymorph (II)

Cs—O2ⁱ	2.983 (4)
Cs—O3ⁱⁱ	3.151 (4)
Cs—O1	3.190 (4)
Cs—O4	3.318 (4)
Cs—O4ⁱⁱⁱ	3.009 (3)
Cs—O5^iv	3.030 (3)
Cs—O5^v	3.181 (4)
Cs—O6ⁱⁱ	3.690 (4)
Cs—O7^vi	3.232 (4)
O4—C6	1.260 (6)
O6—C8	1.269 (6)
O7—C4	1.421 (6)
C3—C4	1.534 (7)
C4—C1	1.536 (7)
C4—C5	1.531 (6)
C5—C6	1.403 (7)
C5—C8	1.402 (6)

C3—C4—C1	113.9 (4)
C6—C5—C8	120.0 (4)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y-1, z; (iii) $[-x+{\script{3\over 2}}, -y-{\script{1\over 2}}, -z+2]$ ; (iv) -x+1, -y, -z+2; (v) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (vi) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Table 4
Hydrogen-bond geometry (Å, °) for polymorph (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7⋯O4	0.85 (7)	1.78 (7)	2.567 (5)	154 (6)
O8—H8⋯O6	0.79 (6)	2.03 (6)	2.817 (5)	176 (6)
N2—H2N⋯O8^vii	0.86 (3)	2.04 (3)	2.864 (6)	162 (6)
N1—H1N⋯O6ⁱ	0.85 (3)	2.16 (3)	3.006 (5)	176 (6)
N3—H3N⋯O3^viii	0.83 (3)	2.52 (3)	3.323 (6)	164 (6)
N4—H4N⋯O1^ix	0.84 (3)	2.18 (3)	3.005 (6)	168 (6)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (viii) $[-x+{\script{3\over 2}}]$ , $[-y+{\script{1\over 2}}]$ , -z+2; (ix) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

All H atoms were located in difference Fourier maps. For polymorph (I), their coordinates were refined freely, with U_iso(H) = 1.2U_eq(O,N); the N—H distance range is 0.74 (3)–0.82 (3) Å, and O—H distances are 0.93 (3) Å for the C—OH H atom and 0.72 (3) Å for the water H atom. For polymorph (II), N—H bond lengths were restrained to 0.85 (3) Å, but O—H distances were not restrained; the O—H distances refined to 0.85 (7) Å for the C—OH H atom and 0.79 (6) Å for the water H atom.

Data collection: COLLECT (Nonius, 1998 ) for polymorph (I); SMART (Bruker, 2001 ) for polymorph (II). Cell refinement: EVALCCD (Duisenberg et al., 2003 ) for polymorph (I); SAINT (Bruker, 2001) for polymorph (II). Data reduction: EVALCCD for polymorph (I); SAINT for polymorph (II). For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2001 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg & Putz, 2004 ) and MERCURY (Version 1.4; Bruno et al., 2002 ); software used to prepare material for publication: SHELXTL and local programs.

Supporting information

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S0108270105029318/sk1870sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105029318/sk1870Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270105029318/sk1870IIsup3.hkl

Comment top

Barbituric acid is a simple molecule which has been much studied in recent times due to its propensity to form polymorphs and, as a result, it has been used as a model compound for developing computational polymorph prediction techniques (Lewis et al., 2004). One of the major obstacles to the success of this research has been the partial flexibility of the molecule, which makes successful polymorph modelling particularly tricky (Lewis et al., 2005). Recently, we demonstrated that this molecular flexibility allows the crystal structure of barbituric acid dihydrate to undergo a phase transition at low temperatures (Nichol & Clegg, 2005).

During the preparation of some alkali metal complexes of barbituric acid, we exposed the reaction with caesium hydroxide to more vigorous conditions than had been used for Li–Rb in order to reduce the solution volume. The result was an unexpected barbiturate coupling product, 5-hydroxyhydurilic acid (5-hydroxy-5,5'-bibarbituric acid) (see scheme), which coordinated in its anionic form to caesium. Repeating the reaction but with only brief heating of the reaction solution gave a normal barbiturate complex, as for the other alkali metals. We have also observed this same coupling when 1,8-bis(dimethylamino)naphthalene (a proton sponge) was used as the base in a methanolic solution of barbituric acid, so the actual base and solvent used would not seem to be determining factors for the reaction. 5-Hydroxyhydurilic acid itself is rather unusual; it is not commercially available and the only reported synthesis to date is by electrochemical oxidation of hydurilic acid (and so not actually a barbiturate coupling reaction; Kato et al., 1975).

Crystallization of the reaction product gave two polymorphic forms, (I) and (II). Crystallization by slow solvent evaporation gave polymorph (I) in the orthorhombic space group Pbcn (reported here in the alternative setting Pnab, so that the axes match those in the second polymorph); space group determination was unambiguous from the systematic absences. The structural unit of polymorph (I) is presented in Fig. 1 and is twice the size of the asymmetric unit. It consists of two Cs–5-hydroxyhydurilate complexes related by a twofold rotation about a non-coordinated but hydrogen-bonded water molecule. The water molecule acts as a donor in two O—H···O interactions and as an acceptor in two N—H···O interactions (Table 2) and so is pseudo-tetrahedral. Additional intramolecular hydrogen bonding secures the location of the OH group into an R₁¹(6) ring (Bernstein et al., 1995). The Cs ion is nine-coordinate (not shown in full in Fig. 1) and the Cs—O bond lengths range from the relatively short 2.981 (2) Å to the rather long 3.531 (2) Å (Table 1). One of the rings of the 5-hydroxyhydurilate ligand is essentially planar (r.m.s deviation from a mean plane fitted through the non-H atoms is 0.012 Å), as is usually observed in deprotonated barbituric acid, whilst the second ring contains an sp³-hybridized C atom, which is displaced slightly out of the ring of the remaining non-H atoms (r.m.s deviation 0.078 Å); the angle between the two mean planes is 85.6 (2)°. The two new bonds formed in the coupling reaction are C4–C5 and C4–O7, which have lengths of 1.502 (4) and 1.439 (3) Å, respectively, indicating that both are single bonds. The hydroxy H atom was easily located in a difference electron-density map, confirming that the C4—O7 bond is single in character. In the planar ring, bonding is delocalized over the O4—C6—C5—C8—O6 segment, with each bond intermediate between single and double.

A monoclinic polymorph, (II), was obtained by storing the solution at approximately 278 K for several months. Although the unit-cell parameters of polymorph (II) are similar to those of polymorph (I), this is for a C-centred rather than a primitive unit cell. The structural unit of polymorph (II) is shown in Fig. 2. Like polymorph (I), polymorph (II) crystallizes with one non-coordinating water molecule on a twofold rotation axis, and so the asymmetric unit is one half of the structural unit. Also, as in polymorph (I), the water molecule is secured in place by four hydrogen bonds, as donor for two and as acceptor for the other two, with additional intramolecular hydrogen bonding securing the position of the hydroxy H atom (Table 4). The Cs ion is again nine-coordinate, but the range of bond lengths is much wider, from 2.983 (4) to 3.690 (4) Å (Table 3), which is distinctly long for a Cs—O bond, but not unknown. The two 5-hydroxyhydurilate rings are either essentially planar (r.m.s deviation 0.007 Å for one) or slightly distorted (r.m.s deviation 0.090 Å for the other), as is seen in polymorph (I), although in polymorph (II), the angle between their two mean planes is slightly smaller, at 78.3 (2)°. Also in common with polymorph (I), the C4—C5 and C4—O7 bond lengths are 1.531 (6) and 1.421 (6) Å, respectively, indicating single-bond character.

If the individual structural units of polymorphs (I) and (II) give little indication that these are two different polymorphic structures, then their respective packing diagrams are more revealing. Fig. 3 shows two b-axis projections of polymorph (I) (top) and polymorph (II) (bottom). Setting polymorph (I) in space group Pnab allows a direct comparison to be made between the two, as the cell axes are now approximately equal. Both are three-dimensional structures featuring columns of quadruply bridged Cs centres. These columns are then linked together by further coordination from the second ring of the ligand across to a Cs centre of another column. This linkage creates what appear to be channels within the structure, sandwiched inside which are securely hydrogen-bonded pseudo-tetrahedral water molecules. Inspection of space-filling models, however, shows that the water molecules lie in individual cavities, between which there are only restricted openings. The differences between the two packing diagrams are in the overall arrangement of the cations, anions and water molecules, and in the shape of the cavities. These are most easily seen by concentrating on the water-filled cavities. In polymorph (I), these apparent channels are arranged such that the overall impression is one of `ripples' within the structure along the c axis. In polymorph (II), there is no such rippling and the apparent channels are stacked ladder-like in a regular rectangular grid.

Experimental top

Computing details top

Data collection: COLLECT (Nonius, 1998) for (I); SMART (Bruker, 2001) for (II). Cell refinement: EVALCCD (Duisenberg et al., 2003) for (I); SAINT (Bruker, 2001) for (II). Data reduction: EVALCCD for (I); SAINT for (II). For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg & Putz, 2004) and Mercury (Version 1.4; Bruno et al., 2002); software used to prepare material for publication: SHELXTL and local programs.

Figures top

	Fig. 1. The structural unit of polymorph (I), with 50% probability displacement ellipsoids. Dashed blue lines indicate selected hydrogen bonds.
	Fig. 2. The structural unit of polymorph (II), with 50% probability displacement ellipsoids. Dashed blue lines indicate selected hydrogen bonds.
	Fig. 3. Packing diagrams, projected along the b axes, for polymorph (I) (top) and polymorph (II) (bottom).

(I) poly[[caesium-µ₅-5-hydroxyhydurilato] hemihydrate] top

Crystal data top

[Cs(C₈H₅N₄O₇)]·0.5H₂O	F(000) = 1576
M_r = 411.08	D_x = 2.397 Mg m⁻³
Orthorhombic, Pnab	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2bc 2n	Cell parameters from 19019 reflections
a = 13.6671 (8) Å	θ = 2.5–27.5°
b = 7.0632 (4) Å	µ = 3.30 mm⁻¹
c = 23.5991 (17) Å	T = 150 K
V = 2278.1 (2) Å³	Block, colourless
Z = 8	0.30 × 0.10 × 0.10 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	2592 independent reflections
Radiation source: sealed tube	2146 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ and ω scans	θ_max = 27.5°, θ_min = 5.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→17
T_min = 0.681, T_max = 0.723	k = −9→8
49241 measured reflections	l = −30→30

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.025	Hydrogen site location: difference Fourier map
wR(F²) = 0.047	Only H-atom coordinates refined
S = 1.05	w = 1/[σ²(F_o²) + (0.0137P)² + 4.4877P] where P = (F_o² + 2F_c²)/3
2592 reflections	(Δ/σ)_max < 0.001
204 parameters	Δρ_max = 0.68 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Cs(C₈H₅N₄O₇)]·0.5H₂O	V = 2278.1 (2) Å³
M_r = 411.08	Z = 8
Orthorhombic, Pnab	Mo Kα radiation
a = 13.6671 (8) Å	µ = 3.30 mm⁻¹
b = 7.0632 (4) Å	T = 150 K
c = 23.5991 (17) Å	0.30 × 0.10 × 0.10 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	2592 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2146 reflections with I > 2σ(I)
T_min = 0.681, T_max = 0.723	R_int = 0.065
49241 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.047	Only H-atom coordinates refined
S = 1.05	Δρ_max = 0.68 e Å⁻³
2592 reflections	Δρ_min = −0.45 e Å⁻³
204 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cs	0.039034 (13)	0.16344 (2)	0.162529 (7)	0.01976 (6)
O1	0.27214 (15)	0.0371 (3)	0.13963 (9)	0.0246 (5)
O2	0.40390 (15)	0.0331 (3)	−0.03639 (8)	0.0228 (5)
O3	0.45309 (15)	0.5577 (3)	0.06914 (8)	0.0225 (5)
O4	0.42089 (15)	0.4654 (3)	0.23028 (8)	0.0234 (5)
O5	0.13690 (15)	0.8022 (3)	0.23249 (8)	0.0236 (5)
O6	0.19927 (14)	0.4358 (3)	0.07812 (8)	0.0194 (4)
O7	0.46294 (14)	0.2385 (3)	0.14908 (8)	0.0187 (4)
H7	0.454 (2)	0.306 (5)	0.1827 (15)	0.022*
O8	0.2500	0.7135 (4)	0.0000	0.0225 (7)
H8	0.226 (3)	0.647 (5)	0.0188 (15)	0.027*
N1	0.34024 (18)	0.0346 (3)	0.05267 (10)	0.0175 (5)
H1N	0.320 (2)	−0.060 (5)	0.0459 (14)	0.021*
N2	0.42811 (18)	0.2934 (3)	0.01760 (10)	0.0169 (5)
H2N	0.456 (2)	0.336 (5)	−0.0055 (14)	0.020*
N3	0.27789 (18)	0.6291 (4)	0.22977 (11)	0.0194 (5)
H3N	0.290 (2)	0.664 (5)	0.2590 (15)	0.023*
N4	0.16987 (18)	0.6193 (3)	0.15560 (10)	0.0169 (5)
H4N	0.121 (2)	0.658 (4)	0.1398 (14)	0.020*
C1	0.3226 (2)	0.1149 (4)	0.10423 (11)	0.0149 (6)
C2	0.3914 (2)	0.1144 (4)	0.00827 (11)	0.0165 (6)
C3	0.42043 (19)	0.3970 (4)	0.06569 (11)	0.0139 (5)
C4	0.37791 (19)	0.2995 (4)	0.11806 (11)	0.0141 (6)
C5	0.31484 (19)	0.4330 (4)	0.15152 (11)	0.0136 (5)
C6	0.34233 (19)	0.5046 (4)	0.20429 (11)	0.0167 (6)
C7	0.1912 (2)	0.6910 (4)	0.20785 (12)	0.0175 (6)
C8	0.22785 (19)	0.4917 (4)	0.12570 (11)	0.0153 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs	0.02383 (10)	0.01822 (9)	0.01723 (9)	−0.00228 (8)	−0.00056 (7)	0.00095 (8)
O1	0.0319 (12)	0.0226 (11)	0.0193 (10)	−0.0079 (9)	0.0064 (9)	0.0016 (9)
O2	0.0303 (12)	0.0246 (11)	0.0134 (10)	−0.0041 (9)	0.0021 (8)	−0.0054 (9)
O3	0.0316 (12)	0.0190 (10)	0.0169 (10)	−0.0105 (9)	0.0076 (9)	−0.0016 (8)
O4	0.0197 (10)	0.0317 (12)	0.0190 (10)	0.0031 (9)	−0.0066 (8)	−0.0039 (9)
O5	0.0223 (11)	0.0243 (12)	0.0242 (11)	0.0024 (9)	0.0049 (8)	−0.0047 (9)
O6	0.0210 (11)	0.0215 (10)	0.0158 (10)	−0.0015 (8)	−0.0061 (8)	−0.0008 (8)
O7	0.0171 (10)	0.0239 (10)	0.0151 (10)	0.0048 (9)	−0.0030 (8)	−0.0026 (8)
O8	0.0307 (18)	0.0145 (15)	0.0222 (17)	0.000	0.0016 (13)	0.000
N1	0.0231 (13)	0.0122 (12)	0.0170 (12)	−0.0060 (10)	0.0028 (10)	−0.0023 (10)
N2	0.0208 (12)	0.0195 (13)	0.0103 (11)	−0.0066 (10)	0.0048 (9)	0.0020 (10)
N3	0.0200 (13)	0.0227 (13)	0.0153 (12)	0.0015 (10)	−0.0036 (10)	−0.0056 (10)
N4	0.0138 (12)	0.0190 (12)	0.0180 (12)	0.0022 (9)	−0.0033 (10)	−0.0006 (10)
C1	0.0149 (14)	0.0140 (13)	0.0159 (13)	0.0005 (11)	0.0004 (11)	0.0024 (10)
C2	0.0154 (13)	0.0190 (14)	0.0150 (13)	0.0011 (11)	−0.0029 (11)	−0.0002 (11)
C3	0.0116 (12)	0.0167 (13)	0.0134 (13)	0.0007 (11)	−0.0005 (10)	0.0012 (11)
C4	0.0122 (13)	0.0173 (14)	0.0129 (13)	0.0004 (11)	0.0000 (10)	0.0008 (10)
C5	0.0114 (12)	0.0168 (13)	0.0125 (13)	−0.0026 (10)	0.0025 (10)	0.0017 (10)
C6	0.0160 (14)	0.0169 (13)	0.0171 (13)	−0.0032 (12)	0.0008 (11)	0.0008 (12)
C7	0.0171 (14)	0.0175 (14)	0.0180 (14)	−0.0041 (12)	0.0036 (11)	−0.0009 (11)
C8	0.0160 (14)	0.0145 (13)	0.0156 (13)	−0.0043 (11)	0.0024 (10)	0.0025 (12)

Geometric parameters (Å, º) top

Cs—O1	3.352 (2)	O7—Cs^xi	3.040 (2)
Cs—O2ⁱ	3.2119 (19)	O7—H7	0.93 (3)
Cs—O3ⁱⁱ	3.1808 (19)	O7—C4	1.439 (3)
Cs—O4ⁱⁱⁱ	3.1361 (19)	O8—H8	0.72 (3)
Cs—O4ⁱⁱ	3.469 (2)	N1—H1N	0.74 (3)
Cs—O5^iv	2.981 (2)	N1—C1	1.364 (4)
Cs—O5^v	3.320 (2)	N1—C2	1.380 (4)
Cs—O6	3.531 (2)	N2—H2N	0.73 (3)
Cs—O7^vi	3.040 (2)	N2—C2	1.379 (4)
Cs—N4	3.687 (2)	N2—C3	1.354 (4)
Cs—C6ⁱⁱ	3.701 (3)	N3—H3N	0.75 (3)
Cs—C8	3.576 (3)	N3—C6	1.382 (4)
O1—C1	1.214 (3)	N3—C7	1.365 (4)
O2—Csⁱ	3.2119 (19)	N4—H4N	0.82 (3)
O2—C2	1.212 (3)	N4—C7	1.365 (4)
O3—Cs^vii	3.1808 (19)	N4—C8	1.392 (3)
O3—C3	1.222 (3)	C1—Cs^xi	3.809 (3)
O4—Cs^viii	3.1361 (19)	C1—C4	1.542 (4)
O4—Cs^vii	3.469 (2)	C3—C4	1.530 (4)
O4—C6	1.267 (3)	C4—C5	1.502 (4)
O5—Cs^ix	2.981 (2)	C5—C6	1.395 (4)
O5—Cs^x	3.320 (2)	C5—C8	1.399 (4)
O5—C7	1.227 (3)	C6—Cs^vii	3.701 (3)
O6—C8	1.253 (3)	C7—Cs^ix	3.704 (3)

O1—Cs—O2ⁱ	62.84 (5)	Csⁱ—O2—C2	134.80 (18)
O1—Cs—O3ⁱⁱ	113.83 (5)	Cs^vii—O3—C3	139.11 (18)
O1—Cs—O4ⁱⁱⁱ	122.83 (5)	Cs^viii—O4—Cs^vii	110.57 (6)
O1—Cs—O4ⁱⁱ	135.87 (5)	Cs^viii—O4—C6	152.89 (17)
O1—Cs—O5^iv	78.18 (5)	Cs^vii—O4—C6	90.36 (16)
O1—Cs—O5^v	59.52 (5)	Cs^ix—O5—Cs^x	119.02 (6)
O1—Cs—O6	57.63 (5)	Cs^ix—O5—C7	117.05 (17)
O1—Cs—O7^vi	93.42 (5)	Cs^x—O5—C7	119.99 (17)
O1—Cs—N4	76.37 (5)	Cs—O6—C8	81.91 (15)
O1—Cs—C6ⁱⁱ	154.41 (6)	Cs^xi—O7—H7	115 (2)
O1—Cs—C8	56.47 (6)	Cs^xi—O7—C4	127.48 (15)
O2ⁱ—Cs—O3ⁱⁱ	67.97 (5)	H7—O7—C4	100.2 (19)
O2ⁱ—Cs—O4ⁱⁱⁱ	142.13 (5)	H1N—N1—C1	120 (3)
O2ⁱ—Cs—O4ⁱⁱ	139.17 (5)	H1N—N1—C2	113 (3)
O2ⁱ—Cs—O5^iv	139.06 (5)	C1—N1—C2	126.7 (2)
O2ⁱ—Cs—O5^v	98.21 (5)	H2N—N2—C2	117 (3)
O2ⁱ—Cs—O6	58.84 (5)	H2N—N2—C3	116 (3)
O2ⁱ—Cs—O7^vi	73.67 (5)	C2—N2—C3	127.0 (2)
O2ⁱ—Cs—N4	95.24 (5)	H3N—N3—C6	118 (3)
O2ⁱ—Cs—C6ⁱⁱ	127.21 (5)	H3N—N3—C7	115 (3)
O2ⁱ—Cs—C8	77.60 (6)	C6—N3—C7	126.3 (2)
O3ⁱⁱ—Cs—O4ⁱⁱⁱ	123.26 (5)	Cs—N4—H4N	85 (2)
O3ⁱⁱ—Cs—O4ⁱⁱ	71.31 (5)	Cs—N4—C7	112.82 (16)
O3ⁱⁱ—Cs—O5^iv	122.54 (5)	Cs—N4—C8	74.52 (14)
O3ⁱⁱ—Cs—O5^v	165.74 (5)	H4N—N4—C7	118 (2)
O3ⁱⁱ—Cs—O6	60.04 (5)	H4N—N4—C8	117 (2)
O3ⁱⁱ—Cs—O7^vi	112.32 (5)	C7—N4—C8	125.2 (2)
O3ⁱⁱ—Cs—N4	66.89 (5)	Cs^xi—C1—O1	87.64 (16)
O3ⁱⁱ—Cs—C6ⁱⁱ	61.57 (5)	Cs^xi—C1—N1	88.28 (16)
O3ⁱⁱ—Cs—C8	72.34 (6)	Cs^xi—C1—C4	88.79 (14)
O4ⁱⁱⁱ—Cs—O4ⁱⁱ	66.92 (3)	O1—C1—N1	121.7 (2)
O4ⁱⁱⁱ—Cs—O5^iv	69.88 (5)	O1—C1—C4	121.0 (2)
O4ⁱⁱⁱ—Cs—O5^v	65.37 (5)	N1—C1—C4	117.0 (2)
O4ⁱⁱ—Cs—O5^iv	65.00 (5)	O2—C2—N1	122.6 (2)
O4ⁱⁱ—Cs—O5^v	122.61 (5)	O2—C2—N2	121.4 (3)
O4ⁱⁱⁱ—Cs—O6	158.85 (5)	N1—C2—N2	116.0 (2)
O4ⁱⁱ—Cs—O6	97.87 (5)	O3—C3—N2	121.9 (3)
O4ⁱⁱⁱ—Cs—O7^vi	68.72 (5)	O3—C3—C4	120.2 (2)
O4ⁱⁱ—Cs—O7^vi	126.48 (5)	N2—C3—C4	117.6 (2)
O4ⁱⁱⁱ—Cs—N4	122.61 (5)	O7—C4—C1	104.5 (2)
O4ⁱⁱ—Cs—N4	65.56 (5)	O7—C4—C3	103.8 (2)
O4ⁱⁱⁱ—Cs—C6ⁱⁱ	66.11 (6)	O7—C4—C5	112.6 (2)
O4ⁱⁱ—Cs—C6ⁱⁱ	20.02 (5)	C1—C4—C3	113.3 (2)
O4ⁱⁱⁱ—Cs—C8	139.09 (6)	C1—C4—C5	111.1 (2)
O4ⁱⁱ—Cs—C8	87.59 (5)	C3—C4—C5	111.1 (2)
O5^iv—Cs—O5^v	70.04 (3)	C4—C5—C6	122.8 (2)
O5^iv—Cs—O6	90.65 (5)	C4—C5—C8	116.4 (2)
O5^v—Cs—O6	116.71 (5)	C6—C5—C8	120.7 (2)
O5^iv—Cs—O7^vi	123.18 (5)	Cs^vii—C6—O4	69.61 (15)
O5^v—Cs—O7^vi	58.14 (5)	Cs^vii—C6—N3	100.12 (17)
O5^iv—Cs—N4	62.10 (5)	Cs^vii—C6—C5	100.81 (16)
O5^v—Cs—N4	119.85 (5)	O4—C6—N3	117.9 (2)
O5^iv—Cs—C6ⁱⁱ	84.05 (6)	O4—C6—C5	125.5 (3)
O5^v—Cs—C6ⁱⁱ	130.32 (5)	N3—C6—C5	116.6 (2)
O5^iv—Cs—C8	70.43 (6)	Cs^ix—C7—O5	45.79 (14)
O5^v—Cs—C8	109.17 (6)	Cs^ix—C7—N3	99.07 (17)
O6—Cs—O7^vi	131.47 (5)	Cs^ix—C7—N4	127.34 (17)
O6—Cs—N4	36.70 (5)	O5—C7—N3	123.4 (3)
O6—Cs—C6ⁱⁱ	104.81 (5)	O5—C7—N4	122.4 (3)
O6—Cs—C8	20.29 (5)	N3—C7—N4	114.1 (2)
O7^vi—Cs—N4	167.66 (5)	Cs—C8—O6	77.80 (15)
O7^vi—Cs—C6ⁱⁱ	111.78 (6)	Cs—C8—N4	83.44 (15)
O7^vi—Cs—C8	145.78 (6)	Cs—C8—C5	108.39 (16)
N4—Cs—C6ⁱⁱ	79.09 (6)	O6—C8—N4	118.7 (2)
N4—Cs—C8	22.04 (6)	O6—C8—C5	124.2 (2)
C6ⁱⁱ—Cs—C8	100.26 (6)	N4—C8—C5	117.1 (2)
Cs—O1—C1	121.99 (17)

O2ⁱ—Cs—O1—C1	57.6 (2)	O7—C4—C5—C8	−176.8 (2)
O3ⁱⁱ—Cs—O1—C1	11.1 (2)	C1—C4—C5—C6	123.4 (3)
O4ⁱⁱⁱ—Cs—O1—C1	−165.9 (2)	C1—C4—C5—C8	−59.9 (3)
O4ⁱⁱ—Cs—O1—C1	−76.2 (2)	C3—C4—C5—C6	−109.4 (3)
O5^iv—Cs—O1—C1	−109.5 (2)	C3—C4—C5—C8	67.3 (3)
O5^v—Cs—O1—C1	176.9 (2)	Cs^viii—O4—C6—Cs^vii	141.6 (4)
O6—Cs—O1—C1	−11.07 (19)	Cs^viii—O4—C6—N3	50.7 (5)
O7^vi—Cs—O1—C1	127.3 (2)	Cs^vii—O4—C6—N3	−90.9 (2)
N4—Cs—O1—C1	−45.7 (2)	Cs^viii—O4—C6—C5	−129.5 (3)
C6ⁱⁱ—Cs—O1—C1	−62.5 (3)	Cs^vii—O4—C6—C5	88.9 (3)
C8—Cs—O1—C1	−35.3 (2)	C7—N3—C6—Cs^vii	106.3 (3)
O1—Cs—O6—C8	−80.13 (16)	C7—N3—C6—O4	178.5 (3)
O2ⁱ—Cs—O6—C8	−155.75 (17)	C7—N3—C6—C5	−1.3 (4)
O3ⁱⁱ—Cs—O6—C8	123.30 (16)	C4—C5—C6—Cs^vii	71.6 (3)
O4ⁱⁱⁱ—Cs—O6—C8	17.9 (2)	C4—C5—C6—O4	−1.0 (4)
O4ⁱⁱ—Cs—O6—C8	60.25 (16)	C4—C5—C6—N3	178.8 (2)
O5^iv—Cs—O6—C8	−4.60 (16)	C8—C5—C6—Cs^vii	−105.0 (2)
O5^v—Cs—O6—C8	−72.49 (16)	C8—C5—C6—O4	−177.5 (3)
O7^vi—Cs—O6—C8	−142.36 (15)	C8—C5—C6—N3	2.2 (4)
N4—Cs—O6—C8	32.43 (15)	Cs^x—O5—C7—Cs^ix	−157.5 (2)
C6ⁱⁱ—Cs—O6—C8	79.42 (16)	Cs^ix—O5—C7—N3	−67.8 (3)
O1—Cs—N4—C7	−98.52 (18)	Cs^x—O5—C7—N3	134.8 (2)
O1—Cs—N4—C8	23.66 (14)	Cs^ix—O5—C7—N4	112.6 (2)
O2ⁱ—Cs—N4—C7	−158.92 (18)	Cs^x—O5—C7—N4	−44.9 (3)
O2ⁱ—Cs—N4—C8	−36.74 (15)	C6—N3—C7—Cs^ix	137.9 (2)
O3ⁱⁱ—Cs—N4—C7	137.74 (19)	C6—N3—C7—O5	−179.9 (3)
O3ⁱⁱ—Cs—N4—C8	−100.09 (15)	C6—N3—C7—N4	−0.2 (4)
O4ⁱⁱⁱ—Cs—N4—C7	22.0 (2)	Cs—N4—C7—Cs^ix	−36.4 (2)
O4ⁱⁱ—Cs—N4—C7	58.62 (18)	Cs—N4—C7—O5	−92.7 (3)
O4ⁱⁱⁱ—Cs—N4—C8	144.13 (14)	Cs—N4—C7—N3	87.6 (2)
O4ⁱⁱ—Cs—N4—C8	−179.20 (16)	C8—N4—C7—Cs^ix	−123.1 (2)
O5^iv—Cs—N4—C7	−14.84 (17)	C8—N4—C7—O5	−179.4 (3)
O5^v—Cs—N4—C7	−56.32 (19)	C8—N4—C7—N3	0.9 (4)
O5^iv—Cs—N4—C8	107.33 (16)	Cs—O6—C8—N4	−75.4 (2)
O5^v—Cs—N4—C8	65.85 (16)	Cs—O6—C8—C5	104.1 (3)
O6—Cs—N4—C7	−151.9 (2)	Cs—N4—C8—O6	72.2 (2)
O6—Cs—N4—C8	−29.71 (13)	Cs—N4—C8—C5	−107.3 (2)
O7^vi—Cs—N4—C7	−133.3 (2)	C7—N4—C8—Cs	107.3 (2)
O7^vi—Cs—N4—C8	−11.2 (3)	C7—N4—C8—O6	179.5 (2)
C6ⁱⁱ—Cs—N4—C7	74.16 (18)	C7—N4—C8—C5	0.0 (4)
C6ⁱⁱ—Cs—N4—C8	−163.67 (16)	C4—C5—C8—Cs	89.6 (2)
C8—Cs—N4—C7	−122.2 (3)	C4—C5—C8—O6	2.1 (4)
Cs—O1—C1—Cs^xi	171.96 (11)	C4—C5—C8—N4	−178.4 (2)
Cs—O1—C1—N1	−101.5 (3)	C6—C5—C8—Cs	−93.6 (2)
Cs—O1—C1—C4	84.8 (3)	C6—C5—C8—O6	178.9 (3)
C2—N1—C1—Cs^xi	−97.9 (3)	C6—C5—C8—N4	−1.6 (4)
C2—N1—C1—O1	176.0 (3)	O1—Cs—C8—O6	86.57 (16)
C2—N1—C1—C4	−10.1 (4)	O1—Cs—C8—N4	−152.10 (17)
Csⁱ—O2—C2—N1	160.72 (18)	O1—Cs—C8—C5	−35.73 (16)
Csⁱ—O2—C2—N2	−19.5 (4)	O2ⁱ—Cs—C8—O6	21.09 (15)
C3—N2—C2—O2	−178.8 (3)	O2ⁱ—Cs—C8—N4	142.42 (15)
C3—N2—C2—N1	1.0 (4)	O2ⁱ—Cs—C8—C5	−101.21 (18)
C1—N1—C2—O2	180.0 (3)	O3ⁱⁱ—Cs—C8—O6	−49.46 (15)
C1—N1—C2—N2	0.2 (4)	O3ⁱⁱ—Cs—C8—N4	71.87 (15)
Cs^vii—O3—C3—N2	−151.2 (2)	O3ⁱⁱ—Cs—C8—C5	−171.76 (19)
Cs^vii—O3—C3—C4	22.9 (4)	O4ⁱⁱⁱ—Cs—C8—O6	−170.23 (13)
C2—N2—C3—O3	−177.6 (3)	O4ⁱⁱ—Cs—C8—O6	−120.60 (15)
C2—N2—C3—C4	8.1 (4)	O4ⁱⁱⁱ—Cs—C8—N4	−48.90 (18)
Cs^xi—O7—C4—C1	11.7 (3)	O4ⁱⁱ—Cs—C8—N4	0.73 (15)
Cs^xi—O7—C4—C3	−107.34 (19)	O4ⁱⁱⁱ—Cs—C8—C5	67.5 (2)
Cs^xi—O7—C4—C5	132.43 (18)	O4ⁱⁱ—Cs—C8—C5	117.10 (17)
O3—C3—C4—O7	−78.2 (3)	O5^iv—Cs—C8—O6	175.12 (17)
O3—C3—C4—C1	169.0 (2)	O5^v—Cs—C8—O6	115.59 (15)
O3—C3—C4—C5	43.0 (3)	O5^iv—Cs—C8—N4	−63.55 (15)
N2—C3—C4—O7	96.1 (3)	O5^v—Cs—C8—N4	−123.09 (14)
N2—C3—C4—C1	−16.7 (3)	O5^iv—Cs—C8—C5	52.82 (17)
N2—C3—C4—C5	−142.7 (2)	O5^v—Cs—C8—C5	−6.71 (19)
Cs^xi—C1—C4—O7	−7.38 (16)	O6—Cs—C8—N4	121.3 (2)
Cs^xi—C1—C4—C3	105.00 (19)	O6—Cs—C8—C5	−122.3 (3)
Cs^xi—C1—C4—C5	−129.05 (18)	O7^vi—Cs—C8—O6	54.5 (2)
O1—C1—C4—O7	79.1 (3)	O7^vi—Cs—C8—N4	175.78 (13)
O1—C1—C4—C3	−168.5 (2)	O7^vi—Cs—C8—C5	−67.8 (2)
O1—C1—C4—C5	−42.5 (3)	N4—Cs—C8—O6	−121.3 (2)
N1—C1—C4—O7	−94.8 (3)	N4—Cs—C8—C5	116.4 (2)
N1—C1—C4—C3	17.5 (3)	C6ⁱⁱ—Cs—C8—O6	−105.03 (15)
N1—C1—C4—C5	143.5 (2)	C6ⁱⁱ—Cs—C8—N4	16.30 (16)
O7—C4—C5—C6	6.5 (4)	C6ⁱⁱ—Cs—C8—C5	132.67 (17)

Symmetry codes: (i) −x+1/2, y, −z; (ii) x−1/2, −y+1, z; (iii) x−1/2, −y+1/2, −z+1/2; (iv) x, y−1/2, −z+1/2; (v) x, y−1, z; (vi) x−1/2, −y, z; (vii) x+1/2, −y+1, z; (viii) x+1/2, −y+1/2, −z+1/2; (ix) x, y+1/2, −z+1/2; (x) x, y+1, z; (xi) x+1/2, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O4	0.93 (3)	1.65 (3)	2.563 (3)	164 (3)
O8—H8···O6	0.72 (3)	2.08 (3)	2.780 (3)	163 (4)
N1—H1N···O8^v	0.74 (3)	2.16 (3)	2.865 (3)	161 (3)
N2—H2N···O3^xii	0.73 (3)	2.09 (3)	2.816 (3)	174 (3)
N3—H3N···O1^ix	0.75 (3)	2.57 (3)	3.151 (3)	136 (3)
N4—H4N···O7ⁱⁱ	0.82 (3)	2.29 (3)	3.005 (3)	147 (3)

Symmetry codes: (ii) x−1/2, −y+1, z; (v) x, y−1, z; (ix) x, y+1/2, −z+1/2; (xii) −x+1, −y+1, −z.

(II) poly[[caesium-µ₅-5-hydroxyhydurilato] hemihydrate] top

Crystal data top

[Cs(C₈H₅N₄O₇)]·0.5H₂O	F(000) = 1576
M_r = 411.08	D_x = 2.381 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7338 reflections
a = 12.1244 (16) Å	θ = 3.0–28.2°
b = 8.1353 (11) Å	µ = 3.28 mm⁻¹
c = 23.267 (3) Å	T = 150 K
β = 91.654 (2)°	Block, colourless
V = 2294.0 (5) Å³	0.30 × 0.18 × 0.15 mm
Z = 8

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2765 independent reflections
Radiation source: sealed tube	2661 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
thin–slice ω scans	θ_max = 28.2°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −16→15
T_min = 0.494, T_max = 0.612	k = −10→10
10061 measured reflections	l = −30→30

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: difference Fourier map
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.42	w = 1/[σ²(F_o²) + 28.7093P] where P = (F_o² + 2F_c²)/3
2765 reflections	(Δ/σ)_max = 0.001
204 parameters	Δρ_max = 1.49 e Å⁻³
4 restraints	Δρ_min = −2.50 e Å⁻³

Crystal data top

[Cs(C₈H₅N₄O₇)]·0.5H₂O	V = 2294.0 (5) Å³
M_r = 411.08	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 12.1244 (16) Å	µ = 3.28 mm⁻¹
b = 8.1353 (11) Å	T = 150 K
c = 23.267 (3) Å	0.30 × 0.18 × 0.15 mm
β = 91.654 (2)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	2765 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2661 reflections with I > 2σ(I)
T_min = 0.494, T_max = 0.612	R_int = 0.031
10061 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	4 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.42	w = 1/[σ²(F_o²) + 28.7093P] where P = (F_o² + 2F_c²)/3
2765 reflections	Δρ_max = 1.49 e Å⁻³
204 parameters	Δρ_min = −2.50 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cs	0.69061 (2)	−0.30528 (4)	0.917618 (12)	0.01215 (9)
O1	0.8404 (3)	−0.0961 (5)	0.83409 (16)	0.0196 (8)
O2	0.8860 (3)	0.2939 (6)	0.70033 (16)	0.0266 (9)
O3	0.8878 (3)	0.4636 (5)	0.88516 (17)	0.0211 (8)
O4	0.7836 (3)	0.0344 (4)	0.98136 (15)	0.0159 (7)
O5	0.4318 (3)	0.2246 (5)	0.97422 (15)	0.0167 (8)
O6	0.6450 (3)	0.3386 (5)	0.82163 (15)	0.0165 (8)
O7	0.9269 (3)	0.1364 (5)	0.91048 (15)	0.0154 (7)
H7	0.896 (5)	0.085 (8)	0.938 (3)	0.019*
O8	0.5000	0.1546 (6)	0.7500	0.0146 (10)
H8	0.539 (5)	0.210 (8)	0.769 (3)	0.018*
N1	0.8440 (4)	0.1048 (5)	0.76762 (18)	0.0139 (8)
H1N	0.843 (5)	0.031 (6)	0.742 (2)	0.017*
N2	0.8803 (4)	0.3796 (5)	0.79307 (18)	0.0136 (8)
H2N	0.903 (5)	0.473 (5)	0.781 (2)	0.016*
N3	0.6087 (3)	0.1294 (5)	0.97575 (17)	0.0116 (8)
H3N	0.603 (5)	0.089 (7)	1.0081 (15)	0.014*
N4	0.5413 (3)	0.2792 (5)	0.89897 (18)	0.0127 (8)
H4N	0.488 (4)	0.328 (7)	0.883 (2)	0.015*
C1	0.8411 (4)	0.0502 (6)	0.8229 (2)	0.0112 (9)
C2	0.8711 (4)	0.2631 (6)	0.7504 (2)	0.0127 (9)
C3	0.8710 (4)	0.3536 (6)	0.8503 (2)	0.0127 (9)
C4	0.8408 (4)	0.1805 (6)	0.8707 (2)	0.0114 (9)
C5	0.7280 (4)	0.1863 (6)	0.8985 (2)	0.0102 (8)
C6	0.7122 (4)	0.1135 (6)	0.9523 (2)	0.0119 (9)
C7	0.5211 (4)	0.2129 (6)	0.9513 (2)	0.0118 (9)
C8	0.6408 (4)	0.2701 (5)	0.8705 (2)	0.0102 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs	0.01245 (14)	0.01435 (15)	0.00964 (14)	0.00019 (12)	0.00023 (9)	0.00157 (12)
O2	0.031 (2)	0.035 (2)	0.0134 (18)	−0.0100 (19)	−0.0027 (16)	0.0075 (18)
O3	0.024 (2)	0.0163 (19)	0.023 (2)	−0.0057 (15)	0.0065 (16)	−0.0072 (16)
O1	0.0238 (19)	0.0135 (18)	0.0218 (19)	−0.0005 (15)	0.0029 (15)	−0.0001 (15)
O4	0.0141 (17)	0.0186 (18)	0.0151 (17)	0.0039 (14)	0.0005 (14)	0.0064 (14)
O5	0.0131 (17)	0.020 (2)	0.0169 (17)	0.0025 (14)	0.0044 (14)	−0.0008 (15)
O6	0.0131 (16)	0.022 (2)	0.0146 (17)	−0.0003 (14)	0.0024 (13)	0.0061 (14)
O7	0.0087 (16)	0.026 (2)	0.0114 (16)	0.0046 (14)	−0.0030 (13)	0.0031 (15)
O8	0.020 (3)	0.008 (2)	0.016 (3)	0.000	−0.002 (2)	0.000
N2	0.016 (2)	0.010 (2)	0.015 (2)	−0.0021 (16)	0.0030 (16)	0.0041 (16)
N1	0.018 (2)	0.014 (2)	0.0103 (19)	−0.0032 (17)	0.0018 (16)	−0.0031 (16)
N3	0.0127 (19)	0.0124 (19)	0.0099 (19)	0.0019 (15)	0.0025 (15)	0.0037 (16)
N4	0.0097 (19)	0.012 (2)	0.016 (2)	0.0031 (15)	−0.0001 (15)	0.0037 (16)
C2	0.006 (2)	0.018 (2)	0.014 (2)	−0.0028 (17)	−0.0002 (17)	0.0030 (19)
C3	0.006 (2)	0.015 (2)	0.017 (2)	0.0002 (17)	0.0027 (17)	−0.0027 (19)
C4	0.011 (2)	0.013 (2)	0.010 (2)	−0.0011 (18)	0.0001 (17)	−0.0014 (18)
C1	0.007 (2)	0.013 (2)	0.013 (2)	−0.0016 (17)	0.0007 (17)	0.0007 (18)
C5	0.008 (2)	0.010 (2)	0.013 (2)	0.0001 (17)	0.0034 (16)	−0.0014 (18)
C6	0.013 (2)	0.009 (2)	0.014 (2)	−0.0004 (17)	0.0008 (18)	−0.0007 (18)
C7	0.014 (2)	0.011 (2)	0.011 (2)	0.0000 (18)	−0.0004 (17)	0.0017 (18)
C8	0.014 (2)	0.006 (2)	0.011 (2)	−0.0024 (16)	0.0001 (17)	−0.0004 (17)

Geometric parameters (Å, º) top

Cs—O2ⁱ	2.983 (4)	O7—Cs^x	3.232 (3)
Cs—O3ⁱⁱ	3.151 (4)	O7—H7	0.85 (7)
Cs—O1	3.190 (4)	O7—C4	1.421 (6)
Cs—O4	3.318 (4)	O8—H8	0.79 (6)
Cs—O4ⁱⁱⁱ	3.009 (3)	N2—H2N	0.86 (3)
Cs—O5^iv	3.030 (3)	N2—C2	1.375 (7)
Cs—O5^v	3.181 (4)	N2—C3	1.356 (6)
Cs—O6ⁱⁱ	3.690 (4)	N1—H1N	0.85 (3)
Cs—O7^vi	3.232 (4)	N1—C2	1.391 (6)
Cs—C3ⁱⁱ	3.890 (5)	N1—C1	1.363 (6)
Cs—C6	3.509 (5)	N3—H3N	0.83 (3)
Cs—C8ⁱⁱ	3.669 (5)	N3—C6	1.389 (6)
O2—Cs^vii	2.983 (4)	N3—C7	1.371 (6)
O2—C2	1.209 (6)	N4—H4N	0.84 (3)
O3—Cs^viii	3.151 (4)	N4—C7	1.360 (6)
O3—C3	1.221 (6)	N4—C8	1.395 (6)
O1—C1	1.218 (6)	C3—Cs^viii	3.890 (5)
O4—Csⁱⁱⁱ	3.009 (3)	C3—C4	1.534 (7)
O4—C6	1.260 (6)	C4—C1	1.536 (7)
O5—Cs^iv	3.030 (3)	C4—C5	1.531 (6)
O5—Cs^ix	3.181 (4)	C5—C6	1.403 (7)
O5—C7	1.225 (6)	C5—C8	1.402 (6)
O6—Cs^viii	3.690 (4)	C8—Cs^viii	3.669 (4)
O6—C8	1.269 (6)

O2ⁱ—Cs—O3ⁱⁱ	99.15 (11)	C3ⁱⁱ—Cs—C8ⁱⁱ	45.40 (10)
O2ⁱ—Cs—O1	57.50 (11)	C6—Cs—C8ⁱⁱ	173.37 (11)
O2ⁱ—Cs—O4ⁱⁱⁱ	155.34 (12)	Cs^vii—O2—C2	141.1 (4)
O2ⁱ—Cs—O4	106.18 (11)	Cs^viii—O3—C3	118.9 (3)
O2ⁱ—Cs—O5^iv	123.96 (10)	Cs—O1—C1	131.2 (3)
O2ⁱ—Cs—O5^v	128.18 (11)	Cs—O4—Csⁱⁱⁱ	81.93 (9)
O2ⁱ—Cs—O6ⁱⁱ	67.56 (10)	Cs—O4—C6	88.0 (3)
O2ⁱ—Cs—O7^vi	73.21 (11)	Csⁱⁱⁱ—O4—C6	142.2 (3)
O2ⁱ—Cs—C3ⁱⁱ	89.20 (11)	Cs^iv—O5—Cs^ix	83.92 (8)
O2ⁱ—Cs—C6	88.17 (12)	Cs^iv—O5—C7	147.0 (3)
O2ⁱ—Cs—C8ⁱⁱ	86.30 (11)	Cs^ix—O5—C7	128.9 (3)
O3ⁱⁱ—Cs—O1	73.91 (10)	Cs^viii—O6—C8	79.2 (3)
O3ⁱⁱ—Cs—O4ⁱⁱⁱ	75.84 (10)	Cs^x—O7—H7	119 (4)
O3ⁱⁱ—Cs—O4	110.70 (9)	Cs^x—O7—C4	134.7 (3)
O3ⁱⁱ—Cs—O5^iv	136.19 (10)	H7—O7—C4	106 (4)
O3ⁱⁱ—Cs—O5^v	56.63 (9)	H2N—N2—C2	114 (4)
O3ⁱⁱ—Cs—O6ⁱⁱ	59.20 (9)	H2N—N2—C3	119 (4)
O3ⁱⁱ—Cs—O7^vi	131.05 (10)	C2—N2—C3	126.5 (4)
O3ⁱⁱ—Cs—C3ⁱⁱ	15.96 (10)	H1N—N1—C2	117 (4)
O3ⁱⁱ—Cs—C6	125.60 (10)	H1N—N1—C1	116 (4)
O3ⁱⁱ—Cs—C8ⁱⁱ	59.08 (10)	C2—N1—C1	126.0 (4)
O1—Cs—O4	68.65 (9)	H3N—N3—C6	115 (4)
O1—Cs—O4ⁱⁱⁱ	139.32 (10)	H3N—N3—C7	119 (4)
O1—Cs—O5^iv	133.75 (10)	C6—N3—C7	125.5 (4)
O1—Cs—O5^v	71.27 (10)	H4N—N4—C7	116 (4)
O1—Cs—O6ⁱⁱ	97.36 (9)	H4N—N4—C8	119 (4)
O1—Cs—O7^vi	128.81 (10)	C7—N4—C8	125.7 (4)
O1—Cs—C3ⁱⁱ	78.38 (10)	O2—C2—N2	122.8 (5)
O1—Cs—C6	65.29 (10)	O2—C2—N1	120.8 (5)
O1—Cs—C8ⁱⁱ	114.33 (10)	N2—C2—N1	116.4 (4)
O4—Cs—O4ⁱⁱⁱ	98.07 (9)	Cs^viii—C3—O3	45.2 (3)
O4ⁱⁱⁱ—Cs—O5^iv	61.81 (10)	Cs^viii—C3—N2	110.4 (3)
O4ⁱⁱⁱ—Cs—O5^v	69.55 (9)	Cs^viii—C3—C4	112.9 (3)
O4—Cs—O5^iv	67.46 (9)	O3—C3—N2	121.4 (5)
O4—Cs—O5^v	56.97 (9)	O3—C3—C4	120.3 (4)
O4ⁱⁱⁱ—Cs—O6ⁱⁱ	89.81 (9)	N2—C3—C4	118.3 (4)
O4—Cs—O6ⁱⁱ	165.33 (8)	O7—C4—C3	104.8 (4)
O4ⁱⁱⁱ—Cs—O7^vi	91.69 (9)	O7—C4—C1	106.3 (4)
O4—Cs—O7^vi	117.91 (9)	O7—C4—C5	112.4 (4)
O4ⁱⁱⁱ—Cs—C3ⁱⁱ	79.98 (10)	C3—C4—C1	113.9 (4)
O4—Cs—C3ⁱⁱ	125.89 (9)	C3—C4—C5	109.1 (4)
O4—Cs—C6	21.03 (10)	C1—C4—C5	110.3 (4)
O4ⁱⁱⁱ—Cs—C6	114.61 (11)	O1—C1—N1	121.4 (5)
O4ⁱⁱⁱ—Cs—C8ⁱⁱ	70.29 (10)	O1—C1—C4	121.3 (4)
O4—Cs—C8ⁱⁱ	165.59 (9)	N1—C1—C4	117.3 (4)
O5^iv—Cs—O5^v	96.08 (9)	C4—C5—C6	120.7 (4)
O5^iv—Cs—O6ⁱⁱ	127.18 (9)	C4—C5—C8	119.3 (4)
O5^v—Cs—O6ⁱⁱ	115.49 (8)	C6—C5—C8	120.0 (4)
O5^iv—Cs—O7^vi	64.34 (9)	Cs—C6—O4	70.9 (3)
O5^v—Cs—O7^vi	158.22 (9)	Cs—C6—N3	96.8 (3)
O5^iv—Cs—C3ⁱⁱ	141.58 (10)	Cs—C6—C5	102.5 (3)
O5^v—Cs—C3ⁱⁱ	72.58 (10)	O4—C6—N3	116.8 (4)
O5^iv—Cs—C6	68.53 (11)	O4—C6—C5	125.9 (4)
O5^v—Cs—C6	76.64 (10)	N3—C6—C5	117.3 (4)
O5^iv—Cs—C8ⁱⁱ	111.82 (10)	O5—C7—N3	122.8 (4)
O5^v—Cs—C8ⁱⁱ	109.70 (10)	O5—C7—N4	122.9 (4)
O6ⁱⁱ—Cs—O7^vi	73.91 (9)	N3—C7—N4	114.3 (4)
O6ⁱⁱ—Cs—C3ⁱⁱ	43.31 (9)	Cs^viii—C8—O6	81.0 (3)
O6ⁱⁱ—Cs—C6	155.54 (10)	Cs^viii—C8—N4	86.9 (3)
O6ⁱⁱ—Cs—C8ⁱⁱ	19.85 (9)	Cs^viii—C8—C5	101.7 (3)
O7^vi—Cs—C3ⁱⁱ	116.20 (10)	O6—C8—N4	117.4 (4)
O7^vi—Cs—C6	102.80 (10)	O6—C8—C5	125.4 (4)
O7^vi—Cs—C8ⁱⁱ	72.08 (10)	N4—C8—C5	117.2 (4)
C3ⁱⁱ—Cs—C6	138.23 (11)

O2ⁱ—Cs—O1—C1	80.7 (4)	C3—C4—C5—C6	−131.3 (5)
O3ⁱⁱ—Cs—O1—C1	−167.0 (5)	C3—C4—C5—C8	46.6 (6)
O4—Cs—O1—C1	−46.4 (4)	C1—C4—C5—C6	102.9 (5)
O4ⁱⁱⁱ—Cs—O1—C1	−123.5 (4)	C1—C4—C5—C8	−79.2 (5)
O5^iv—Cs—O1—C1	−27.2 (5)	Csⁱⁱⁱ—O4—C6—Cs	−74.1 (4)
O5^v—Cs—O1—C1	−107.4 (4)	Cs—O4—C6—N3	88.1 (4)
O6ⁱⁱ—Cs—O1—C1	138.1 (4)	Csⁱⁱⁱ—O4—C6—N3	13.9 (8)
O7^vi—Cs—O1—C1	62.9 (5)	Cs—O4—C6—C5	−91.8 (5)
C3ⁱⁱ—Cs—O1—C1	177.3 (5)	Csⁱⁱⁱ—O4—C6—C5	−166.0 (4)
C6—Cs—O1—C1	−23.9 (4)	C7—N3—C6—Cs	−109.1 (4)
C8ⁱⁱ—Cs—O1—C1	148.9 (4)	C7—N3—C6—O4	178.8 (5)
O2ⁱ—Cs—O4—Csⁱⁱⁱ	175.49 (9)	C7—N3—C6—C5	−1.3 (7)
O2ⁱ—Cs—O4—C6	32.0 (3)	C4—C5—C6—Cs	−78.0 (4)
O3ⁱⁱ—Cs—O4—Csⁱⁱⁱ	−77.84 (10)	C4—C5—C6—O4	−2.6 (8)
O3ⁱⁱ—Cs—O4—C6	138.7 (3)	C4—C5—C6—N3	177.5 (4)
O1—Cs—O4—Csⁱⁱⁱ	−140.08 (11)	C8—C5—C6—Cs	104.2 (4)
O1—Cs—O4—C6	76.5 (3)	C8—C5—C6—O4	179.5 (5)
O4ⁱⁱⁱ—Cs—O4—Csⁱⁱⁱ	0.0	C8—C5—C6—N3	−0.4 (7)
O4ⁱⁱⁱ—Cs—O4—C6	−143.4 (3)	O2ⁱ—Cs—C6—O4	−149.3 (3)
O5^iv—Cs—O4—Csⁱⁱⁱ	54.87 (9)	O2ⁱ—Cs—C6—N3	94.6 (3)
O5^v—Cs—O4—Csⁱⁱⁱ	−59.12 (9)	O2ⁱ—Cs—C6—C5	−25.4 (3)
O5^iv—Cs—O4—C6	−88.6 (3)	O3ⁱⁱ—Cs—C6—O4	−49.4 (3)
O5^v—Cs—O4—C6	157.4 (3)	O3ⁱⁱ—Cs—C6—N3	−165.4 (2)
O6ⁱⁱ—Cs—O4—Csⁱⁱⁱ	−121.9 (3)	O3ⁱⁱ—Cs—C6—C5	74.6 (3)
O6ⁱⁱ—Cs—O4—C6	94.6 (4)	O1—Cs—C6—O4	−94.6 (3)
O7^vi—Cs—O4—Csⁱⁱⁱ	96.25 (10)	O1—Cs—C6—N3	149.4 (3)
O7^vi—Cs—O4—C6	−47.2 (3)	O1—Cs—C6—C5	29.4 (3)
C3ⁱⁱ—Cs—O4—Csⁱⁱⁱ	−83.43 (12)	O4ⁱⁱⁱ—Cs—C6—O4	40.4 (3)
C3ⁱⁱ—Cs—O4—C6	133.1 (3)	O4—Cs—C6—N3	−116.0 (4)
C6—Cs—O4—Csⁱⁱⁱ	143.4 (3)	O4ⁱⁱⁱ—Cs—C6—N3	−75.6 (3)
C8ⁱⁱ—Cs—O4—Csⁱⁱⁱ	−35.2 (4)	O4—Cs—C6—C5	124.0 (4)
C8ⁱⁱ—Cs—O4—C6	−178.7 (4)	O4ⁱⁱⁱ—Cs—C6—C5	164.4 (3)
Cs^vii—O2—C2—N2	−147.7 (4)	O5^iv—Cs—C6—O4	82.8 (3)
Cs^vii—O2—C2—N1	32.6 (8)	O5^v—Cs—C6—O4	−19.3 (3)
C3—N2—C2—O2	−176.2 (5)	O5^iv—Cs—C6—N3	−33.2 (3)
C3—N2—C2—N1	3.5 (7)	O5^v—Cs—C6—N3	−135.4 (3)
C1—N1—C2—O2	169.8 (5)	O5^iv—Cs—C6—C5	−153.2 (3)
C1—N1—C2—N2	−9.9 (7)	O5^v—Cs—C6—C5	104.6 (3)
Cs^viii—O3—C3—N2	88.2 (5)	O6ⁱⁱ—Cs—C6—O4	−142.4 (2)
Cs^viii—O3—C3—C4	−93.1 (5)	O6ⁱⁱ—Cs—C6—N3	101.5 (3)
C2—N2—C3—Cs^viii	−135.8 (4)	O6ⁱⁱ—Cs—C6—C5	−18.5 (4)
C2—N2—C3—O3	175.1 (5)	O7^vi—Cs—C6—O4	138.3 (3)
C2—N2—C3—C4	−3.7 (7)	O7^vi—Cs—C6—N3	22.3 (3)
Cs^x—O7—C4—C3	−37.8 (5)	O7^vi—Cs—C6—C5	−97.7 (3)
Cs^x—O7—C4—C1	83.1 (5)	C3ⁱⁱ—Cs—C6—O4	−62.6 (3)
Cs^x—O7—C4—C5	−156.1 (3)	C3ⁱⁱ—Cs—C6—N3	−178.7 (2)
Cs^viii—C3—C4—O7	−104.9 (3)	C3ⁱⁱ—Cs—C6—C5	61.3 (3)
Cs^viii—C3—C4—C1	139.4 (3)	Cs^iv—O5—C7—N3	49.0 (9)
Cs^viii—C3—C4—C5	15.7 (4)	Cs^ix—O5—C7—N3	−138.0 (4)
O3—C3—C4—O7	−54.6 (6)	Cs^iv—O5—C7—N4	−132.2 (5)
O3—C3—C4—C1	−170.4 (4)	Cs^ix—O5—C7—N4	40.9 (7)
O3—C3—C4—C5	65.9 (6)	C8—N4—C7—O5	−179.9 (5)
N2—C3—C4—O7	124.1 (4)	C8—N4—C7—N3	−0.9 (7)
N2—C3—C4—C1	8.3 (6)	C6—N3—C7—O5	−179.2 (5)
N2—C3—C4—C5	−115.4 (5)	C6—N3—C7—N4	1.9 (7)
Cs—O1—C1—N1	−132.8 (4)	Cs^viii—O6—C8—N4	81.7 (4)
Cs—O1—C1—C4	48.2 (6)	Cs^viii—O6—C8—C5	−98.1 (5)
C2—N1—C1—O1	−163.7 (5)	C7—N4—C8—Cs^viii	−102.2 (5)
C2—N1—C1—C4	15.3 (7)	C7—N4—C8—O6	179.7 (4)
O7—C4—C1—O1	50.5 (6)	C7—N4—C8—C5	−0.6 (7)
O7—C4—C1—N1	−128.5 (4)	C4—C5—C8—Cs^viii	−84.2 (4)
C3—C4—C1—O1	165.4 (4)	C4—C5—C8—O6	3.0 (7)
C3—C4—C1—N1	−13.6 (6)	C4—C5—C8—N4	−176.7 (4)
C5—C4—C1—O1	−71.6 (6)	C6—C5—C8—Cs^viii	93.7 (4)
C5—C4—C1—N1	109.4 (5)	C6—C5—C8—O6	−179.1 (5)
O7—C4—C5—C6	−15.5 (6)	C6—C5—C8—N4	1.2 (7)
O7—C4—C5—C8	162.4 (4)

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) x, y−1, z; (iii) −x+3/2, −y−1/2, −z+2; (iv) −x+1, −y, −z+2; (v) x+1/2, y−1/2, z; (vi) x−1/2, y−1/2, z; (vii) −x+3/2, y+1/2, −z+3/2; (viii) x, y+1, z; (ix) x−1/2, y+1/2, z; (x) x+1/2, y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O4	0.85 (7)	1.78 (7)	2.567 (5)	154 (6)
O8—H8···O6	0.79 (6)	2.03 (6)	2.817 (5)	176 (6)
N2—H2N···O8^x	0.86 (3)	2.04 (3)	2.864 (6)	162 (6)
N1—H1N···O6ⁱ	0.85 (3)	2.16 (3)	3.006 (5)	176 (6)
N3—H3N···O3^xi	0.83 (3)	2.52 (3)	3.323 (6)	164 (6)
N4—H4N···O1^ix	0.84 (3)	2.18 (3)	3.005 (6)	168 (6)

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ix) x−1/2, y+1/2, z; (x) x+1/2, y+1/2, z; (xi) −x+3/2, −y+1/2, −z+2.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Cs(C₈H₅N₄O₇)]·0.5H₂O	[Cs(C₈H₅N₄O₇)]·0.5H₂O
M_r	411.08	411.08
Crystal system, space group	Orthorhombic, Pnab	Monoclinic, C2/c
Temperature (K)	150	150
a, b, c (Å)	13.6671 (8), 7.0632 (4), 23.5991 (17)	12.1244 (16), 8.1353 (11), 23.267 (3)
α, β, γ (°)	90, 90, 90	90, 91.654 (2), 90
V (Å³)	2278.1 (2)	2294.0 (5)
Z	8	8
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	3.30	3.28
Crystal size (mm)	0.30 × 0.10 × 0.10	0.30 × 0.18 × 0.15

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.681, 0.723	0.494, 0.612
No. of measured, independent and observed [I > 2σ(I)] reflections	49241, 2592, 2146	10061, 2765, 2661
R_int	0.065	0.031
(sin θ/λ)_max (Å⁻¹)	0.650	0.665

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.047, 1.05	0.044, 0.082, 1.42
No. of reflections	2592	2765
No. of parameters	204	204
No. of restraints	0	4
H-atom treatment	Only H-atom coordinates refined	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0137P)² + 4.4877P] where P = (F_o² + 2F_c²)/3	w = 1/[σ²(F_o²) + 28.7093P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.45	1.49, −2.50

Computer programs: COLLECT (Nonius, 1998), SMART (Bruker, 2001), EVALCCD (Duisenberg et al., 2003), SAINT (Bruker, 2001), EVALCCD, SAINT, SHELXTL (Sheldrick, 2001), DIAMOND (Brandenburg & Putz, 2004) and Mercury (Version 1.4; Bruno et al., 2002), SHELXTL and local programs.

Selected geometric parameters (Å, º) for (I) top

Cs—O1	3.352 (2)	O4—C6	1.267 (3)
Cs—O2ⁱ	3.2119 (19)	O6—C8	1.253 (3)
Cs—O3ⁱⁱ	3.1808 (19)	O7—C4	1.439 (3)
Cs—O4ⁱⁱⁱ	3.1361 (19)	C1—C4	1.542 (4)
Cs—O4ⁱⁱ	3.469 (2)	C3—C4	1.530 (4)
Cs—O5^iv	2.981 (2)	C4—C5	1.502 (4)
Cs—O5^v	3.320 (2)	C5—C6	1.395 (4)
Cs—O6	3.531 (2)	C5—C8	1.399 (4)
Cs—O7^vi	3.040 (2)

C1—C4—C3	113.3 (2)	C6—C5—C8	120.7 (2)

Symmetry codes: (i) −x+1/2, y, −z; (ii) x−1/2, −y+1, z; (iii) x−1/2, −y+1/2, −z+1/2; (iv) x, y−1/2, −z+1/2; (v) x, y−1, z; (vi) x−1/2, −y, z.

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O4	0.93 (3)	1.65 (3)	2.563 (3)	164 (3)
O8—H8···O6	0.72 (3)	2.08 (3)	2.780 (3)	163 (4)
N1—H1N···O8^v	0.74 (3)	2.16 (3)	2.865 (3)	161 (3)
N2—H2N···O3^vii	0.73 (3)	2.09 (3)	2.816 (3)	174 (3)
N3—H3N···O1^viii	0.75 (3)	2.57 (3)	3.151 (3)	136 (3)
N4—H4N···O7ⁱⁱ	0.82 (3)	2.29 (3)	3.005 (3)	147 (3)

Symmetry codes: (ii) x−1/2, −y+1, z; (v) x, y−1, z; (vii) −x+1, −y+1, −z; (viii) x, y+1/2, −z+1/2.

Selected geometric parameters (Å, º) for (II) top

Cs—O2ⁱ	2.983 (4)	O4—C6	1.260 (6)
Cs—O3ⁱⁱ	3.151 (4)	O6—C8	1.269 (6)
Cs—O1	3.190 (4)	O7—C4	1.421 (6)
Cs—O4	3.318 (4)	C3—C4	1.534 (7)
Cs—O4ⁱⁱⁱ	3.009 (3)	C4—C1	1.536 (7)
Cs—O5^iv	3.030 (3)	C4—C5	1.531 (6)
Cs—O5^v	3.181 (4)	C5—C6	1.403 (7)
Cs—O6ⁱⁱ	3.690 (4)	C5—C8	1.402 (6)
Cs—O7^vi	3.232 (4)

C3—C4—C1	113.9 (4)	C6—C5—C8	120.0 (4)

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) x, y−1, z; (iii) −x+3/2, −y−1/2, −z+2; (iv) −x+1, −y, −z+2; (v) x+1/2, y−1/2, z; (vi) x−1/2, y−1/2, z.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O4	0.85 (7)	1.78 (7)	2.567 (5)	154 (6)
O8—H8···O6	0.79 (6)	2.03 (6)	2.817 (5)	176 (6)
N2—H2N···O8^vii	0.86 (3)	2.04 (3)	2.864 (6)	162 (6)
N1—H1N···O6ⁱ	0.85 (3)	2.16 (3)	3.006 (5)	176 (6)
N3—H3N···O3^viii	0.83 (3)	2.52 (3)	3.323 (6)	164 (6)
N4—H4N···O1^ix	0.84 (3)	2.18 (3)	3.005 (6)	168 (6)

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (vii) x+1/2, y+1/2, z; (viii) −x+3/2, −y+1/2, −z+2; (ix) x−1/2, y+1/2, z.

Acknowledgements

The authors thank the EPSRC for funding.

References

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ISSN: 2053-2296

Volume 61| Part 10| October 2005| Pages m459-m462

doi:10.1107/S0108270105029318